Fluoropolymer composition

ABSTRACT

Fluoropolymer compositions containing melt-fabricable functionalized fluoropolymer and liquid crystal polymer have enhanced adhesion to metal even at low concentrations of liquid crystal polymer.

RELATED APPLICATION

This is a division of application Ser. No. 09/114,636 filed Jul. 13,1998, now U.S. Pat. No. 6,166,138.

This application claims the benefit of Provisional Application No.60/058,286 filed Sep. 9, 1997.

FIELD OF THE INVENTION

This invention is in the field of melt-fabricable fluoropolymers, and isspecifically concerned with melt-fabricable fluoropolymer compositionshaving enhanced properties.

BACKGROUND OF THE INVENTION

Fluoropolymer resins, and especially perfluoropolymer resins, are knownfor their low surface energy and antistick properties and thermal andchemical resistance. These copolymers do not stick to other materials,especially dissimilar materials, with any practical degree of bondstrength.

Some high temperature resistant thermoplastics (HTRP), such as polyamideimide, polyarylene sulfide and polyether sulfone, have found use asadhesion promoters in fluoropolymer coating formulations. See, forexample U.S. Pat. No. 5,230,961 (Tannenbaum) and U.S. Pat. No. 5,093,403(Rau et al.). While liquid crystal polymers (LCP) have been included inHTRP groupings for other purposes, LCP are not known as adhesionpromoters. While LCP can exhibit some adhesion to metal in the neat(undiluted) state, such adhesion is much less than exhibited by therecognized HTRP adhesion promoters.

There remains a need for melt-flowable fluoropolymer with improvedadhesion to dissimilar materials but which substantially retains thethermal and chemical resistance of fluoropolymer.

SUMMARY OF THE INVENTION

This invention provides a melt-fabricable fluoropolymer compositioncomprising minor amounts of functionalized fluoropolymer and liquidcrystal polymer, and a major amount of non-functional fluoropolymer. Thecomposition exhibits synergistic enhanced adhesion to metal, enablingone to use relatively low concentrations of liquid crystal polymer toachieve adhesion, so that the composition has predominantlyfluoropolymer character. Heretofore, liquid crystal polymer has not beenknown as an adhesion promoter.

In a further embodiment, the invention provides a laminate of metal andthe melt-fabricable composition of the invention adhered thereto.

DETAILED DESCRIPTION

It has been discovered that a combination of functionalizedfluoropolymer and liquid crystal polymer (LCP) results in a synergisticincrease in the adhesion of the resultant fluoropolymer composition tometal. When both components are present, the adhesion result is betterthan would be predicted from adhesion results when only one of thesecomponents is present, and, as shown below, is better than the adhesionof neat LCP. As a result, relatively low concentrations of LCP can beused to achieve good adhesion, so that the composition has a relativelyhigh proportion of fluoropolymer and, therefore, predominantlyfluoropolymer characteristics.

As used herein, “functionalized fluoropolymer” means fluoropolymerhaving functional side groups or functional groups attached to sidegroups. Usually, but not necessarily, such functional units are at theends of the pendant side groups. Functional groups, in the context ofthe present invention, are groups capable of enhancing the effect of LCPas an adhesion promoter, when functional groups and LCP are both presentin a fluoropolymer composition, to achieve an adhesive bond between thefluoropolymer composition and a metal surface, e.g., to form a laminate.Such functional groups can be introduced, for example, by incorporatinginto the fluoropolymer, during polymerization, monomer units having suchfunctional groups, i.e., functional monomers.

Functional groups that can enhance the effect of LCP as an adhesionpromoter include ester, alcohol, acid (including carbon-, sulfur-, andphosphorus-based acid) and salt and halide thereof. Otherfunctionalities include cyanate, carbamate, nitrile, and the like.Specific functional groups that can be used include —SO₂F, —CN, —COOHand —CH₂—Z wherein —Z is —OH, —OCN, —O—(CO)—NH₂, or —OP(O)(OH)₂.Preferred functional groups include —SO₂F and —CH₂—Z wherein —Z is —OH,—O—(CO)—NH₂, or —OP(O)(OH)₂. The functional groups —CH₂—Z wherein —Z is—OH, —O—(CO)—NH₂ or —OP(O)(OH)₂ are especially preferred. As one skilledin the art will recognize, more than one type of functional group can bepresent. Normally, however, a single type of functional group is used.

The concentration of functional groups in the fluoropolymer resincomponent, i.e., in functionalized fluoropolymer plus non-functionalfluoropolymer, of the melt-fabricable fluoropolymer composition of thisinvention is effective to enhance the effect of LCP as an adhesionpromoter and thereby to enable good adhesion to metal at low LCPconcentration. As will be recognized by one skilled in the art, theconcentration of functional groups that is effective to enhance theeffect of LCP as an adhesion promoter can vary at least with the type offunctional group and with the type of LCP. The concentration offunctional groups present can be expressed relative to the number ofmain chain carbon atoms in the fluoropolymer resin. Generally, theconcentration of functional groups present is at least about 25/10⁶ mainchain C atoms, based on total fluoropolymer in the composition. Theconcentration of functional groups is usually in the range of 25-2500per 10⁶ main chain C atoms, preferably in the range of 50-2000 per 10⁶main chain C atoms, based on total fluoropolymer present.

One skilled in the art will recognize that the desired concentration offunctional groups in the functionalized fluoropolymer resin can beachieved with a single fluoropolymer having functional groups, or amixture of such fluoropolymers having the same or different functionalgroups. However, a single fluoropolymer having only one type offunctional group is normally used. Likewise, the non-functionalfluoropolymer component of the composition can be a blend ofnon-functional fluoropolymers.

Thus, in the present invention, the melt-fabricable fluoropolymercomposition contains minor amounts of functionalized fluoropolymer andliquid crystal polymer resin, and a major amount of non-functionalfluoropolymer. By “major amount” is meant at least 50 wt %, preferablyat least 70 wt %, of non-functional fluoropolymer based on combinedweight of non-functional fluoropolymer, functional fluoropolymer, andLCP. The composition preferably contains 1-30 wt %, more preferably 1-20wt %, most preferably 3-15 wt %, of functionalized fluoropolymer and0.5-15 wt %, more preferably 1-10 wt %, of LCP, based on combined weightof non-functional fluoropolymer, functionalized fluoropolymer, and LCP.Such LCP contents are generally lower than other HTRP contents ofcompositions in which the other HTRP is present for adhesion promotion.The concentration of functional groups in the functionalizedfluoropolymer alone will be higher than recited above for totalfluoropolymer according to the amount of non-functional fluoropolymerpresent in the blend.

Fluoropolymer resins that can be used include copolymers of TFE with oneor more copolymerizable monomers chosen from perfluoroolefins having 3-8carbon atoms and perfluoro(alkyl vinyl ethers) (PAVE) in which thelinear or branched alkyl group contains 1-5 carbon atoms. Preferredperfluoropolymers include copolymers of TFE with at least one ofhexafluoropropylene (HFP) and PAVE. Preferred comonomers include PAVE inwhich the alkyl group contains 1-3 carbon atoms, especially 2-3 carbonatoms, i.e. perfluoro(ethyl vinyl ether) (PEVE) and perfluoro(propylvinyl ether) (PPVE). Additional fluoropolymers that can be used includecopolymers of ethylene with TFE, optionally including minor amounts ofone or more modifying comonomer such as perfluorobutyl ethylene.Representative fluoropolymers are described, for example, in ASTMStandard Specifications D-2116, D-3159, and D-3307. Such fluoropolymersare non-functional fluoropolymers if they have essentially no functionalgroups, but are functionalized fluoropolymers if functional groups areadded, e.g., by grafting. Preferred fluoropolymers areperfluoropolymers, except for functional units or groups. Alternativelyor additionally, preferred fluoropolymers are non-elastomeric, asopposed to elastomeric.

Functionalized fluoropolymers include fluoropolymers such as thosedescribed in the foregoing paragraph and additionally containingcopolymerized units derived from functional monomers. If theconcentration of functional monomer is high enough in a TFE copolymer,however, no other comonomer may be needed. Usually, but not necessarily,the functional groups introduced by such monomers are at the ends ofpendant side groups. Functional monomers that introduce pendant sidegroups having such functionality can have the general formula CY₂═CY—Zwherein Y is H or F and Z contains a functional group. Preferably, eachY is F and —Z is —R_(f)—X, wherein R_(f) is a fluorinated diradical andX is a functional group that may contain CH₂ groups. Preferably, R_(f)is linear or branched perfluoroalkoxy having 2-20 carbon atoms, so thatthe functional comonomer is a fluorinated vinyl ether. Examples of suchfluorovinylethers include CF₂═ CF[OCF₂CF(CF₃)]_(m)—O—(CF₂)_(n)CH₂OH asdisclosed in U.S. Pat. No. 4,982,009 and the alcoholic esterCF₂═CF[OCF₂CF(CF₃)]—O—(CF₂)_(n)—(CH₂)_(p)—O—COR as disclosed in U.S.Pat. No. 5,310,838. Additional fluorovinylethers includeCF₂═CF[OCF₂CF(CF₃)]_(m)O(CF₂)_(n)COOH and its carboxylic esterCF₂═CF[OCF₂CF(CF₃)]_(m)O(CF₂)_(n)COOR disclosed in U.S. Pat. No.4,138,426. In these formulae, m=0-3, n=1-4, p=1-2 and R is methyl orethyl. Preferred such fluorovinylethers include CF₂═CF—O—CF₂CF₂—SO₂F;CF₂═CF[OCF₂CF(CF₃)]O(CF₂)₂—Y wherein —Y is —SO₂F, —CN, or —COOH; andCF₂═CF[OCF₂CF(CF₃)]O(CF₂)₂—CH₂—Z wherein —Z is —OH, —OCN, —O—(CO)—NH₂,or —OP(O)(OH)₂. These fluorovinylethers are preferred because of theirability to incorporate into the polymer and their ability to incorporatefunctionality into the resultant copolymer.

Compounds having the formula CF₂═CF—R_(f)—(CH₂)_(n)—X in which X is —OCN(cyanate), —O—(CO)—NH₂ (carbarnate), or —OP(O)(OH)₂ (phosphono) can besynthesized as follows. The cyanate can be prepared in high yield by aone-step process in which known compounds having the general formulaCF₂═CF—R_(f)—(CH₂)_(n)—OH (1), wherein n is 1-3 and R_(f) isperfluorolkyl or perfluoroalkoxy containing 1-20 carbon atoms, arereacted with cyanogen bromide (CNBr) or cyanogen chloride (CNCl) in thepresence of non-nucleophilic base. The carbamate can be prepared fromthe cyanate by contacting cyanate with acid at elevated temperature fortime sufficient to complete conversion of cyanate to carbamate. Thephosphorus-containing compounds can be prepared in high yield by aprocess in which compounds (I) are reacted with P(O)CI₃ or P(O)Br₃,either neat or in aprotic solvent, to obtain the chloride or bromide,e.g., CF₂═CF—R_(f)—(CH₂)_(n)—OP(O)(Cl₂), followed by hydrolysis toobtain the acid —OP(O)—(OH)₂. Also see European Patent ApplicationPublication 0 829 471 and PCT Pat. No. Application PublicationWO98/11114 with respect to preparation of these compounds.

When functionalized fluoropolymer is achieved by copolymerization, theamount of functional monomer in the functionalized fluoropolymer of thisinvention is small to achieve the desired concentration of functionalgroups, even when functionalized fluoropolymer is a blend comprisingnon-functional fluoropolymer. Generally, the amount of functionalmonomer is no more than 10 wt %, preferably no more than 5 wt %, basedon total weight of functionalized fluoropolymer, i.e., the fluoropolymercomponent containing the functional monomer. In certain instances,higher concentrations of functional monomer approaching and evenexceeding 10 wt % may be desired, for example, to achieve good bonds tosubstrate metal such as stainless steel, or when it is not desired touse a non-functional monomer in the functionalized melt-fabricablefluoropolymer. While the functionalized fluoropolymer can be uniform, itis not necessary to have a uniform concentration of functional monomerthroughout the functionalized fluoropolymer.

The fluoropolymer composition of this invention is melt-fabricable. Assuch, the composition generally has melt viscosity (MV) in the range of0.5-50×10³ Pa·s though viscosities outside this range can be used. MV ismeasured according to ASTM D-1238 at the temperature appropriate for thepredominant fluoropolymer component of the composition. Preferably, MVis in the range of 1-25×10³ Pa·s. Usually, the MV of each fluoropolymercomponent is within the aforesaid ranges, but blending will permit aminor component to have MV in a wider range, as will be understood byone skilled in the art.

As known in the art, liquid crystal polymers (LCP), also calledthermotropic LCP, are characterized by their unique ability to formregions of high molecular orientational order in the melt. Thisorientation can be carried over into the solid state and the orientationenhanced by appropriate processing techniques that introduce high shearor elongational stresses on the LCP during part fabrication. By“thermotropic LCP”, or equivalently herein “LCP”, is meant a polymerthat when tested by the TOT test as described in U.S. Pat. No. 4,075,262transmits light through crossed polarizers as described in that testprocedure and is thus considered to form an anisotropic melt. Anythermotropic LCP can be used in the melt-fabricable fluoropolymercomposition of this invention. Suitable LCP are described, for examplein U.S. Pat. Nos. 3,991,013; 3,991,014; 4,011,199; 4,048,148; 4,075,262;4,083,829; 4,118,372; 4,122,070; 4,130,545; 4,153,779; 4,159,365;4,161,470; 4,169,933; 4,184,996; 4,189,549; 4,219,461; 4,232,143;4,232,144; 4,245,082; 4,256,624; 4,269,965; 4,272,625; 4,370,466;4,383,105; 4,447,592; 4,522,974; 4,617,369; 4,664,972; 4,684,712;4,727,129; 4,727,131; 4,728,714; 4,749,769; 4,762,907; 4,778,927;4,816,555; 4,849,499; 4,851,496; 4,851,497; 4,857,626; 4,864,013;4,868,278; 4,882,410; 4,923,947; 4,999,416; 5,015,721; 5,015,722;5,025,082; 5,1086,158; 5,102,935; 5,110,896 and U.S. Pat. No. 5,143,956;and European Patent Application 356,226. Useful LCP include polyesters,poly(ester-amides), poly(ester-imides), and polyazomethines. Preferredthermotropic LCP are polyesters or poly(ester-amides), and it isespecially preferred that the polyester or poly(ester-amide) is partlyor fully aromatic. Commercial examples of LCP include the aromaticpolyesters or poly(ester-amides) sold under the trademarks Zenite™(DuPont), Vectra® (Hoechst), and Xydar® (Amoco).

The melt-fabricable fluoropolymer compositions of this invention canhave various forms. They can be melt-mixed compositions, e.g.,compounded using melt processing equipment of conventional design andsuitably equipped for handling fluoropolymers at melt temperatures, suchas twin rotor mixers and extruders with good mixing capability. Thecompositions can also be powder blends, or dispersion or slurry blends.

The fluoropolymer composition can be processed by means, such as knownin the art, appropriate to the physical form of the composition to forma laminate or to prepare the fluoropolymer component of a laminate.Thus, for example, the composition can be extruded or injection molded,or deposited by powder coating techniques such as rotolining orelectrostatic spraying if the composition is a powder, or applied by wetcoating techniques such as roll coating or spraying if the compositionis a dispersion, followed by drying and fusing, and the like.

The melt-fabricable fluoropolymer compositions of this invention exhibitsurprisingly good adhesion to metal at low concentrations of LCP, sinceLCP is not known as adhesion promoter. Good adhesion is indicated by apeel strength of at least 700 g/cm, preferably at least 1000 g/cm, whenmeasured in a peel test against aluminum as hereinafter described.Hence, the compositions are useful in laminates either as a primer or asa sole fluoropolymer component. The metal surface can be rough orsmooth. The Example to follow illustrates that the melt-fabricablecomposition of the present invention can adhere to smooth metalsurfaces. As known to those skilled in the art, the adhesion of coatingsto metal can be enhanced by roughening the metal surface, e.g., bysandblasting. Generally, the metal surface should be free of dirt andgrease.

EXAMPLES

Compositions were prepared for testing in laminates by melt compoundingfluoropolymer resins and additives in a laboratory twin-rotor mixer withroller type rotors (Rheomix® 3000, Haake Buechler) controlled and drivenby Haake's Rheocord® 40 microprocessor controlled torque rheometer. Allcomponents of a composition were charged to the mixing chamber together.Temperature and rotor speed were controlled by adjustment within themicroprocessor. The product removed from the mixer after melt blendingwas in relatively large chunks, which were cut into small piecessuitable for molding, or, in some cases, these small pieces were groundinto a powder before molding. The amount of each component in thecomposition is expressed in wt % based on total combined weight ofstated components.

Unless otherwise stated, TFE/PPVE copolymers containing a functionalmonomer were used in the following Examples to illustrate the invention.These functionalized fluoropolymers were prepared by aqueous dispersionpolymerization generally by the method disclosed by Gresham & Vogelpohl(U.S. Pat. No. 3,635,926) using ethane as chain transfer agent, exceptthat a functional monomer was included in the initial charge to thereactor and buffer was not used. Functional monomers employed aredefined in Table 1. Functionalized fluoropolymer solids were isolatedfrom the raw dispersion by mechanical shear coagulation with addition ofwater-immiscible solvent, followed by filtering and drying. Thecompositions of the functionalized fluoropolymers were determined byFourier transform infrared spectroscopy.

TABLE 1 Functional Monomer Identification Code Identification orDescription EVE-OH CF₂═CF—[OCF₂CF(CF₃)]—O—CF₂CF₂—CH₂—OH9,9-dihydro-9-hydroxy-perfluoro(3,6-dioxa-5-methyl-1-nonene) EVE-PCF₂═CF—[OCF₂CF(CF₃)]—O—CF₂CF₂—CH₂—OP(O)(OH)₂9-phosphono-9,9-dihydro-perfluoro(3,6-dioxa-5-methyl-1-nonene)EVE-carbamate CF₂═CF—[OCF₂CF(CF₃)]—O—CF₂CF₂—CH₂—O—(CO)—NH₂9-carbamate-9,9-dihydro-perfluoro(3,6-dioxa-5-methyl-1-nonene)

Unless otherwise stated, the compositions prepared in the followingExamples included a non-functional TFE/PPVE copolymer (PFA) which wasused in cube form as supplied (Teflon® PFA fluoropolymer resin grade340, DuPont). The peel strength measured against aluminum, as describedbelow, for this resin alone was in the range of 185-345 g/cm.

Unless otherwise stated, LCP used in the compositions was a crystallinepolyester, Zenite® liquid crystal polymer resin grade 7000 (DuPont).

Unless otherwise stated, samples were prepared for peel strength testingas follows. A steel plate 0.060-inch (1.5-mm) thick and 8-inch (20.3-cm)square was used as the base for the laminate fabrication. A 0.040-inch(1.0-mm) thick and 8-inch square chase having a 6-inch (15.2-cm) squareopening was placed on the steel plate. The chase was covered with analuminum sheet 0.005 inch (0.13 mm) thick and 8 inches square asreceived from the manufacturer (A. J. Oster Co.), and a 2.5-inch(6.4-cm) wide strip of 0.002-inch (0.05-mm) thick polyimide film(Kapton®, DuPont Co.) was positioned along one edge of the aluminum sothat it overlapped the opening in the chase by about 0.5 inch (1.3 cm).Then, about 65 g of the test resin composition were placed on thealuminum foil within the outline of the opening in the chase. The resinwas covered with another aluminum sheet, and in turn another steelplate. This construction was then compressed in a platen press attemperature and pressure appropriate to the fluoropolymer used. Afterremoval from the press, the laminate was placed between heavy steelplates at room temperature until cool, and then was cut into one-inch(2.5-cm) wide strips.

The peel strength values reported herein were determined as follows. Thelayers of the laminate strips were separated at the polyimide partingfilm, and fastened in the jaws of an Instron® tensile tester. The movingjaw was driven at a speed of one inch/min (2.5 cm/min) to peel thelayers apart, holding the free end of the laminate taking on an angle of180° with respect to the line of the jaws. The average force to peel thestrips apart during the time interval between 30 sec and 100 sec ofpulling was recorded, and is reported in force per unit width of strip.

Example 1 and Controls

The compositions summarized in Table 1 were prepared as described above.The functionalized fluoropolymer (Fcn-FP-1) employed contained 3.2 wt %of PPVE and 8.1 wt % of EVE-OH, and had MV of 1.8×10³ Pa·s. Laminates ofthe compositions and aluminum sheet were prepared and peel strength wasmeasured, also as described above. Results presented in Table 2 showthat adhesion is surprisingly high for the composition containing boththe functionalized fluoropolymer and the LCP. The peel strengthexhibited for Example 1 is more than 50% greater than for the neat LCP,which was determined to be 1072 g/cm.

TABLE 2 Compositions and Results for Example 1 Example/Control A B 1Composition (wt %): Fcn-FP-1 10 — 10 LCP — 10 10 PFA 90 90 80Properties: Peel strength (g/cm) 230  393  1540 

Example 2 and Controls

This example illustrates the present invention for compositionscontaining non-functional fluoropolymer other than PFA. Thenon-functional fluoropolymer was a TFE/HFP copolymer (FEP) satisfyingASTM D-2116 Type I (Teflon® FEP fluoropolymer resin grade 100, DuPont).The functionalized fluoropolymer (Fcn-FP-2) contained 3.6 wt % of PPVEand 3.1 wt % of EVE-OH, and had MV of 6.8×10³ Pa·s. Compositions andresults are shown in Table 3. As shown by the data, adhesion was highfor the composition containing both the functionalized fluoropolymer andthe LCP, showing that different fluoropolymers can be used incompositions of the invention and the functional fluoropolymer need notbe the same type as the non-functional fluoropolymer.

TABLE 3 Compositions and Results for Example 2 Example/Control C D 2Composition (wt %): Fcn-FP-2 10 — 10 LCP — 10 10 FEP 90 90 80Properties: Mv (10³ Pa · s) 7.2 5.9 7.2 Peel Strength (g/cm) 122 0 2232

Examples 3-4 and Controls

These examples illustrate the present invention for functionalizedfluoropolymers containing different functional monomers (EVE-P andEVE-carbamate). Functionalized fluoropolymer Fcn-FP-3 contained 4.3 wt %of PPVE and 0.66 wt % of EVE-P, and had MV of 1.5×10³ Pa·s.Functionalized fluoropolymer Fcn-FP-4 contained 6.7 wt % of PEVE(instead of PPVE) and 1.1 wt % of EVE-carbamate, and had MV of 1.6×10³Pa·s. Compositions and results are shown in Table 4. As shown by thedata, adhesion was high for the compositions containing both thefunctionalized fluoropolymer and the LCP.

TABLE 4 Compositions and Results for Examples 3-4 Example/Control E F 3G 4 Composition (wt %): Fcn-FP-3 2.5 — 2.5 — — Fcn-FP-4 — — — 2.5 2.5LCP — 4.0 4.0 — 4.0 PFA 97.5 96.0 93.5 97.5 93.5 Properties: Mv (10³ Pa· s) 4.5 4.3 3.6 4.2 4.4 Peel Strength (g/cm) 0 523 1,537 268 1661

Examples 5-6 and Controls

These examples illustrate the present invention for compositionscontaining different LCP resins (Zenite® liquid crystal polymer resingrades 1000 and 6000, DuPont). Grade 6000 is less crystalline than andhas a heat distortion temperature 20° C. lower than grade 7000, whilegrade 1000 is an amorphous LCP. The non-functional fluoropolymer was theFEP resin used in Example 2, and the functionalized fluoropolymer wasFcn-FP-2 (also Example 2). Compositions and results are shown in Table5. Adhesion was high for the compositions containing both thefunctionalized fluoropolymer-and LCP resin, showing that different LCPresins can be used in compositions of the invention.

TABLE 5 Compositions and Results for Examples 5-6 Example/Control H I 5J 6 Composition (wt %): Fcn-FP-2 10.0 — 9.5 — 9.5 LCP Zenite ™ 1000 —9.5 9.5 — — LCP Zenite ™ 6000 — — — 9.5 9.5 FEP 90.0 90.5 81.0 90.5 81.0Properties: MV (10³ Pa · s) 7.2 5.8 6.8 6.5 10.4 Peel Strength (g/cm)122 166 1725 675 1358

Examples 7-8 and Controls

These examples illustrates the present invention using type 321stainless steel (SS) foil 0.002 inch (0.051 mm) thick (PTP-512, LyonIndustries) instead of aluminum as the test metal. The foil was clean asreceived from the manufacturer but was also cleaned with acetone anddried. The functionalized fluoropolymer (Fcn-FP-5) contained, 4.3 wt %of PPVE and 1.6 wt % of EVE-OH, and had MV of 0.7×10³ Pa·s. Compositionsand results are shown in Table 6. As shown by the data, adhesion to SSwas high for the composition containing both the functionalizedfluoropolymer and the LCP (Zenite® 7000).

TABLE 5 Compositions and Results for Examples 7-8 Example/Control K L 7M N 8 Composition (wt %): Fcn-FP-5 2.5 — 2.5 2.5 — 2.5 LCP — 4.0 4.0 —4.0 4.0 PFA 97.5 96.0 93.5 97.5 96.0 93.5 Foil Al Al Al SS SS SSProperties: MV (10³ Pa · s) 3.8 4.3 4.5 3.8 4.3 4.5 Peel Strength (g/cm)14 523 2050 320 430 1166

What is claimed is:
 1. A laminate, comprising metal and amelt-fabricable fluoropolymer composition comprising minor amounts offunctionalized fluoropolymer resin and liquid crystal polymer resin anda major amount of non-functionalized fluoropolymer resin adheredthereto.
 2. The laminate according to claim 1, wherein said metal isselected from the group consisting of aluminum and stainless steel. 3.The laminate according to claim 1, wherein the functional group of saidfunctionalized fluoropolymer is at least one of —SO₂F and —CH₂—Z wherein—Z is —OH, —O—(CO)—NH₂, or —OP(O) (OH)₂.
 4. The laminate according toclaim 3, wherein said functional group is —CH₂—OH.
 5. The laminateaccording to claim 3, wherein said functional group is —CH₂—O—(CO)—NH₂.6. The laminate according to claim 3, wherein said functional group is—CH₂—OP(O) (OH)₂.
 7. The laminate according to claim 1, wherein saidliquid crystal polymer resin is present in an amount of 0.5-15 wt %based on combined weights of liquid crystal polymer resin,functionalized fluoropolymer resin, and non-functionalized fluoropolymerresin present.
 8. The laminate according to claim 1, wherein an amountof functional monomer in said functionalized fluoropolymer is no morethan 10 wt %.
 9. The laminate according to claim 1, wherein an amount ofsaid functionalized fluoropolymer in said melt-fabricable fluoropolymercomposition is from 1-30 wt % based on combined weights of liquidcrystal polymer resin, functionalized fluoropolymer resin, andnon-functionalized fluoropolymer resin present.
 10. The laminateaccording to claim 1, wherein an amount of said functionalizedfluoropolymer in said melt-fabricable fluoropolymer composition is from1-30 wt % and said liquid crystal polymer resin is present in an amountof 0.5-15 wt %, based on combined weights of liquid crystal polymerresin, functionalized fluoropolymer resin, and non-functionalizedfluoropolymer resin present.
 11. The laminate according to claim 1,wherein the concentration of functional groups on said functionalizedfluoropolymer is in the range of 25-2500 per 10⁶ main chain carbonatoms.
 12. The laminate according to claim 1, wherein saidmelt-fabricable fluoropolymer composition is interposed between twolayers of said metal.